1:2-metal complexes of monoazo dyes containing a 1, 2-diphenyl-3, 5-diketopyrazolidine coupling component



United States Patent 3,062,806 1:2-METAL COMPLEXES OF MONOAZO DYESCONTAINING A 1,2-DIPHENYL-3,5-DIKETOPY- RAZOLIDINE COUPLING COMPONENTWalter Biedermann and Guido Schetty, Basel, Switzerland, assignors to J.R. Geigy A.-G., Basel, Switzerand No Drawing. Filed Aug. 5, 1960, Ser.No. 47,623 Claims priority, application Switzerland Aug. 7, 1959 4Claims. (Cl. 260-147) The invention concerns metallisable azo dyestuffsand the complex metal compounds thereof, a process for the productionthereof vas well as their use for the dyeing of textile material. Theinvention also concerns, as industrial product, the materials dyed withthese new dyestuffs.

It has been found that valuable metallisable azo dyestuffs are obtainedif diazotised aromatic amines of the benzene and naphthalene serieswhich, in the o-position to the amino group, contain a metallisablegroup or a group which can be converted into such, are coupled with a3,5-diketopyrazolidine and the azo dyestuff obtained, possibly mixedwith any other metallisable azo dyestuif desired, is converted either insubstance or on the fibre, into its metal complex.

Diazotised 2-amino-l-carboxyaryl, Z-amino-l-alkoxyaryl and,advantageously Z-amino-l-hydroxyaryl compounds, in particular of thebenzene series, are used as diazo components. The diazo components usedaccording to the invention can also contain arylazo groups in additionto the substituents usual in azo dyestuffs.

These diazo components are diazotised by the usual methods in mineralacid with alkali nitrite.

As coupling components, the 3,5-diketopyrazolidines coupling in the 4-position, particularly those coupling at the nitrogen atom, i.e.derivatives organically substituted in the 1-' and 2-positions can beused. Preferred dyestulfs are. those from 1,2-disubstituted.derivativesin whichthe N-substituents can be the same asor different from, eachother.

The nitrogen substituents of the coupling components can be alkyl groupssuch as, e;g. the methyl, ethyl, n-

propyl, isopropyl, n-butyl or hexyl group; cycloalkyl' groups such ase.g. the cyclohexyl group; araliphatic groups such as e.g. the benzylgroup; heterocyclic groups such as e.g. the benzthiazolyl-(2) or.thequinoIinyl-(Z) group; and homocyclic aryl groupsfsuch as e.g. naphthylnuclei can contain inert substituents,vfor example halogens such asfluorine, chlorine or bromine; aliphaticgroups such as methyl,ethyl,.isopropyl, tert. butyl or tert..amyl; groups; cycloaliphaticgroups such. as the cyclohexyl group; araliphatic groups such as thebenzyl groups;,homocyclic-aromatic groups such as phenyl, methylphenyl,chlorophenyl or methoxyphenyl groups; ether groups suchv as the methoxy,ethoxy, hydroxyethoxy and phenoxygroups; also nitro, trifluoromethyl,cyano, hydrocarbon carbonyl or acylamino groups, in particular also thegroups improving the Water solubility such as the sulph amyl group andsulphamide groups organically substituted at the nitrogen atom, forexample by lower alkyl, hydroxyalkyl, cycloalkyl, aralkyl orphenyl-.groups,-also sulpl'lamidev groups.

derived from saturated hetero rings.containingnitrogen such aspipe'ridine, morpholine, QrpiperaZine, aswell as low molecular aliphaticsulphonyl groups such as the methyl, chloromethyl, ethyl, isopropyl,hydroxyethyl or- 3,062,806 Patented Nov. 6, 1962 2 vinyl sulphonylgroups. Finally, the dyestuffs according to the invention suitable fortextile dyeing can also 0on tain the usual acid, salt-forming groups,for example the carboxyl or the sulphonic acid group. 7

The azo dyestulfs according to the invention can be converted into theircomplex heavy metal compounds either in substance or on the fibre bytreatment with agents giving off metal, in particular with agents givingoff chromium or also cobalt. The simple or complex chromium salts can beused as agents giving off'ehromirim, for example chromic fluoride,chromic sulphate, chromic acetate, chromic formate, chromic salts ofaryl sulphonic acids and the alkali or ammonium salts ofdisalicylatochromic acids. Also salts of hexavalent chromium can be usedas agents giving off chromium, for example the alkali and ammoniumchromates or bichromates, this particularly when acid wool dyeings arebeing after-chromed or when chroming dyestuffs in substance in thepresence of reducing agents, in particular in the presence of reducingsugars.

The usual salts of-cobalt such ascobalt acetate, cobalt sulphate, cobaltchloride or cobalt hexamminetrichloride are used as agents giving olfcobalt. The presence of complex formers for example of alkali tartrates,is advantageous in-the metallisation process.

The azo dyestuffs according to the invention are metal lised in the mostsimple case, i.e. when they are sufficiently soluble in the reactionmedium, in aqueous solution or suspension at the boil. Often theaddition of organic solubility promoters is indicated, as which can beused, for example, lower alcohols, lower ether alcohols, lower ketonesand amides of lower fatty acids.

If it is intended to produce complex metal compounds which contain twomolecules of the same or different azo dyestuffs to one metal atom, thenthe agents giving off metal is used under such conditions and, possibly,in such amounts, that there is less than one metal atom to one moleculeof azo dyestuff. In this case the metallisation is performedadvantageously in neutral to alkaline medium at temperatures of 140 C.,if necessary under pressure.

However, if it is intended to produce complex metal compounds whichcontain one molecule of azo dyestutf to one metal atom, e.g. a chromiumatom, then the azo dyestutf is treated advantageously with an excess ofthe agent giving off metal, in particular an agent giving off chromium;advantageously in an acid medium at pH values of 2 to 5 and attemperatures of over C. if necessary under pressure. Thechromium-containing dyestuffs which contain 1 metal atom per dyestuffmolecule bound in complex linkage are valuable for the production ofuniform mixed-complexes according to the invention by adding a differentmetallisable dyestulf to the 1:1 complex'in an alkaline medium. 7

Those metal compounds which' contain 1 metal atom to 2 molecules of azodyestuifare-preferred'.

In these so-called 2:1 complexes there should be at most one acid,salt-forming group, not taking part in the complex formation per complexdyestuif molecule, advantageously a sulphonic acid group or, also, acarboxyl group, in the form of their alkali metal or ammonium salts. Thepresence of a sulphonic acid group is favourable if at least one of thedyestuffs bound in complex linkage is a'disazo dye'stufi.

In general, however, 2:1 complexes formed from unsulphonated monoazodyestuffs are preferred for the dyeingof polypeptide fibres from aneutral to weakly acid bath, it being favourable for the dyeingbehaviour when there isa substituent promoting water solubility presentfor each azo group present. This is alsotrue of the 2:1 com-' plexescontaining disazo dyestuffs. In addition to the sulphamyl and suphonylgroups given above as substituents promoting water solubility, alsoacylamino groups derived from low molecular acids, e.g. acetylamino,carbomethoxyamino, methylsulphonylamino, ethylsulphonylamino,chlorosulphonylamino and, possibly, lower ether groups can be used. r

' The suitability of the heavy metal-containing dyestuffs according tothe invention for textile dyeing can be further increased by mixing themwith additives, for example by mixing with capillary active wetting anddispersing agents, alkali phosphates or with salts having an alkalinereaction such as alkali carbonates.

Naturally heavy metal-containing dyestuffs according to the invention ofthe type: two different dyestuif molecules per heavy metal atom, canalso be produced by metallising mixtures of dyestuffs, a component ofwhich mixtures is at least one azo dyestufi as defined.

Depending on their composition, the heavy metal-containing dyestulfsaccording to the invention are suitable for the dyeing of textilematerials from an aqueous bath or in the spinning mass; they are alsosuitable for the dyeing of lacquers and varnishes in light fast yellow,orange, brown to red shades. The water soluble dyestuffs areparticularly suitable for the dyeing of natural or synthetic polypeptidefibres from a neutral to weakly acid bath, for example, for the dyeingof wool, silk, leather, resins, synthetic polyamide and polyurethanefibres. The dyeing attained therewith are distinguished by very goodfastness to light and their evenness as well as by good fastness towashing, sea water, decatising, alkali and rubbing.

Particularly valuable are dyestuffs selected from the class consistingof the azo dyestuffs having the formula wherein:

A represents a benzene radical,

X represents a metallisable group in o-position to the azo groupselected from the group consisting of OH and COOH,

R represents a benzene radical, and

R represents a member selected from the group consisting of hydrogen,lower alkyl and benzene radicals,

and the chromium and cobalt complexes of said dyestuffs containing onemetal atom in complex linkage with two molecules of dyestuff.

Of these, the 2:1 chromium and cobalt complexes of monoazo dyestuffs ofthe above formula are again preferred in which R and R represent thephenyl radical and A contains no sulphonic acid groups or carboxylicacid groups not taking part in the complex formation. However, Aadvantageously contains an alkylsulphonyl or a sulphamide group.

The following examples serve to illustrate the invention. Where nototherwise stated, parts are given as parts by weight and thetemperatures are in degrees centigrade. The relationship of parts byweight to parts by volume is as that of kilogrammes to litres.

Example 1 dyestuff formed is isolated. It corresponds to the formula cON l SOgCH;

formamide and 13.6 parts of chromic acetate, containing 2.9 parts ofchromium, are heated for 3 hours at and the mixture is stirred into 2000parts of a cold 20% sodium chloride solution. The precipitated dyestuff,which corresponds to the formula is filtered off, washed and dried. Itis an orange powder which dyes wool from a neutral to weakly acid bathin orange shades which have good wet fastness properties and very goodfastness to light.

Similar chromium-containing dyestuffs are obtained if the 26 parts of1,2-diphenyl-3,S-diketopyrazolidine are replaced bv 35.0 parts ofl,2-di-(3-nitrophenyl)-3,5-diketopyrazolidine or by 28.8 parts of1,2-di-(4-methylphenyl)-3,5-diketopyrazolidine.

Example 2 45 parts of the metal-free monoazo dyestuff obtained accordingto Example 1 are heated in 1000 parts of water and 30 parts of sodiumcarbonate at 80. A solution of 13.1 parts of crystallised basic cobaltacetate in 52.5 parts of water is added to this solution and the mixtureis kept at 80 until the original dyestuff has disappeared. Thecobalt-containing dyestulf is then salted out, filtered off and dried.It is a brown-yellow powder which dyes wool from a neutral to weaklyacid bath in yellow shades.

Similar cobalt-containing dyestuffs are obtained if in the aboveexample, corresponding amounts of dyestuffs are used which have beenproduced by the process accord ing to Example 1 using 35 parts ofl,2-di-(3'-nitrophenyl)-3,5-diketopyrazolidine, 28.8 parts of l,2-di-(4-methylphenyl)-3,5-diketopyrazolidine, 32.1 parts of 1,2-di-(4-chlorophenyl)-3,5-diketo-pyrazolidine or 31.2 parts of1,2-di-(4'-methoxyphenyl)-3,5-diketopyrazolidine as azo components.

Example 3 13.7 parts of Z-aminobenzene-l-carboxylic acid in 300 parts ofwater and 70 parts of concentrated hydrochloric acid are diazotised at0-5 with the solution of 6.9 parts of sodium nitrite in 20 parts ofwater. At 0-5 the diazonium salt solution is poured into a solution of4.1 parts of sodium hydroxide, 12 parts of sodium carbonate and 26.0parts of 1,2-diphenyl-3,S-diketopyrazolidine in 300 parts of water.After a few hours, the coupling is complete. The dyestuff is filteredoff and dried.

The dry dyestuff is heated for a few hours at 115-120 with 300 parts offormamide and 13.6 parts of chromic acetate, containing 2.9 parts ofchromium. The mixture is then poured into .1200 parts of a 20% sodiumchloride solution, the precipitatedproduct is filtered off, washed anddried. The yellow powder obtained which corresponds to the formula dyeswool and nylon in a neutral to weakly acid bath in yellow shades whichhave good fastness to light.

Similar dyestuffs are obtained if in the above example, instead of 2-amino-1-carboxylic acid, 15.1 parts of 3-methyl-Z-aminobenzene-l-carboxylic acid or 23.0 parts ofZ-aminobenzene-l-carboxylic acid 5 sulphonic acid methylamide are usedas diazo components.

Example 4 The diazoxide, which is obtained by diazotising 29.2 parts of3-amino-4-hydroxyazobenzene-ST-sulphonic acid amide, is suspended in 400parts of water. A solution of 26.0 parts of1,2-diphenyl-3,S-diketopyrazolidine, 4.1 parts of sodium hydroxide andparts of sodium carbonate in 300 parts of water is poured in. When thedyestuff formation is complete, a further 400 parts of water and 38.5parts of the monoazo dyestuff from diazotised 1 hydroxy 2 aminobenzene 4sulphonic acid methyl amide and l-phenyl-B-methyl S-pyrazolone in theform of its sodium salt are added.

The dyestuif mixture is heated to 65-75". A solution of 26.2 parts ofcrystallised basic cobalt acetate in 100 parts of water is addedto themixture and the whole is heated until the. complex formation iscomplete. The dyestuif formed'is salted out, filtered off, washed anddried. It is a brown-yellow powder which dyes wool from a neutral toweakly acid bath in yellow-brown shades. As component, it contains themixed complex of the following constitution:

- so2NHoHi W /O=N NN0 C0 H+ a E I Example 5 256 parts by volume of a 0.5molar aqueous solution of the sodium salt of disalicylato chromic acidare added to a solution of 400 parts of the metal-free azo dyestuffproduced according to paragraph l of Example 3, 45.0 parts of the azodyes-tuif from diazotised Z-amino-l-hydroxybenzene-4-sulphonic acidmethylamide and l-meth- 'ane sulphonylarnino57-hydroxynaphthalene in1500. parts of water and the wholeis heated at 100, is' kept at the boiluntil the complex formation is com plete. The dystuff formed which, ascomponent,-contains the mixed complex of the formula is salted out,filtered off, washed and dried. It dyes wool in olive green shades.

Example-6 18.8 parts of 2-amino-1-hydroxybenzene-5-'sulphonic acid amidein 200 parts of water and 17 partsof concentrated hydr-ochloric acid;are ,diazotised with the solution of 6.9 parts of sodium nitrite in 20parts of water, The suspension of the diazoxide ispoured at.0 into asolu tion consisting of 19.0 parts of 1-phenyl-2-methyl-3,5 di-'ketopyrazolidine, 4.1 parts of sodium hydroxide, 15 parts v of sodiumcarbonate and 30 0 parts of .water. When no more di'azonium compound canbe. traced, 128 parts volume of a 0,5'molar aqueous solution of thesodium salt. of disalicylato chromic acid are. added to the reactionmixture and the mixture is boiled for some hours. "Themetal-containingdyestutf formedfwhich corresponds to) the formulaissalted out, filtered oif, washed and dried. 'Itis an orangepowderwhich dyes wool from a weakly acid bath in red-orange shadeswhich havevery good fastness to light.

Similar dyestuffs are obtained if the coupling comp nent in thisexarnple is replaced by 22.4 parts of 1-(4'- chlorophenyl) 2 methyl3,5-diketopy1'azolidine or by 2 0.4

parts of, l-phenyl 2gethyl-3,5 diketopyrazo1idine.

E amp 7 15.4 parts of 4-nitro- 2-amin o l-hydroxybenzene in 400 parts ofwater and 17 parts of concentrated-hydrochloric acid are dia zotisedwith the solution of 6.9 parts ofisodium nitritein 20 parts of water. Asolution of 18.1 parts of 1-phenyl-3,5-diketopyrazolidine, 4.1-partsofcaustic soda lye and 15 parts of sodium carbonate in 200 parts of wateris poured at 0 into the suspension of the' diazonium compound. When the'dye'stuif formation is complete, the mixture is heated to and asolution of 13.6 parts of crystallised basic cobalt acetate in 52.5parts of- The mixture 7 water is added. On completion of the complexformation, the dystutf is salted out, filtered 01f, washed and dried. Itis a brownish powder which dyes lacquers or spinning masses inbrownish-yellow shades. The com- A similar dyestufi is obtained if thediazo component used in this example is replaced by 14.4 parts of4-chloro- 2-amino-l-hydroxybenzene.

Example 8 22.35 parts of 4-chloro-2-amino-'1-hydroxybenzene-6- sulphonicacid and 4.0 parts of caustic soda lye are dissolved with a neutralreaction in 170 parts of hot water. A solution of 6.9 parts of sodiumnitrite in 100 parts of water is then added, the mixture is cooled to 10and at 0 is added to a mixture of 23 parts of concentrated hydrochloricacid and 23 parts of Water. To the diazonium compound so produced isthen poured at 0 a solution consisting of 26.0 parts of1,2-diphenyl-3,5- diketopyrazolidine, 4.1 parts of sodium hydroxide, 12parts of sodium carbonate and 200 parts of water. The temperature isallowed to reach room temperature within a few hours. When the couplingreaction is complete, the dyestufi is filtered off, Washed and dried. Itis a brown-red powder which corresponds to the formula Dyed onto wool byboth the single bath and the afterchroming process, the dyestuffsproduce beautiful red shades which have good fastness to milling andlight.

Similar dyestuffs are obtained if the above diazo components arereplaced by 23.4 parts of 4-nitro-2-amino-lhydroxybenzene-6-sulphonicacid, 23.4 parts of 6-nitro-2- amino-1-hydroxybenzene-4-sulphonic acidor by 21.7 parts of Z-amino-l-carboxybenzene-S-sulphonic acid.

Example 9 2 parts of the chromium compound according to Example 1 aredissolved in 4000 parts of Water and 1 00 parts of previously wettedwool are introduced into the dyebath at 4050. The bath is brought to theboil within half an hour, kept boiling for 45 minutes and then the woolis rinsed with cold water and dried. The orange dyeing obtained has goodwet fastness properties and good fastness to light.

An equally good dyeing is obtained if the 100 parts of wool are replacedby 100 parts of nylon.

What we claim is:

1. A complex heavy metal compound which contains one atom of a metalselected from the group consisting of cobalt and chromium in complexunion with two azo dyestufi molecules free from sulphonic acid andcarboxylic acid groups not taking part in the complex formation of thegeneral formula wherein A represents a benzene radical and X representsa metallisable group in o-position to the azo group selected from thegroup consisting of OH and -COOH.

2. The complex chromium compound of the formula SIOZCH3 3. The complexcobalt compound of the formula 4. The complex chromium compound of theformula References Cited in the file of this patent UNITED STATESPATENTS 2,427,911 Kendall et al. Sept. 23, 1947 2,908,677 Straley et alOct. 13, 1959 (U.S. counterpart of Canadian patent) FOREIGN PATENTS571,684 Canada Mar. 3, 1959

1. A COMPLEX HEAVY METAL COMPOUND WHICH CONTAINS ONE ATOM OF A METALSELECTED FROM THE GROUP CONSISTING OF COBALT AND CHROMIUM IN COMPLEXUNION WITH TWO AZO DYESTUFF MOLECULES FREE FROM SULPHONIC ACID ANDCARBOXYLIC ACID GROUPS NOT TAKING PART IN THE COMPLEX FORMATION OF THEGENERAL FORMULA